CN104744617A - [5] turil bridged acrylic polymer microsphere, preparation method and application - Google Patents
[5] turil bridged acrylic polymer microsphere, preparation method and application Download PDFInfo
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- CN104744617A CN104744617A CN201510133033.8A CN201510133033A CN104744617A CN 104744617 A CN104744617 A CN 104744617A CN 201510133033 A CN201510133033 A CN 201510133033A CN 104744617 A CN104744617 A CN 104744617A
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- melon
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- bridging acrylate
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- 239000004005 microsphere Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920000058 polyacrylate Polymers 0.000 title abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 36
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001179 sorption measurement Methods 0.000 claims abstract description 15
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 5
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical group N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 claims description 113
- 229920001577 copolymer Polymers 0.000 claims description 63
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 241000219112 Cucumis Species 0.000 claims description 18
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 13
- 238000000502 dialysis Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229920002125 Sokalan® Polymers 0.000 claims description 7
- 239000004584 polyacrylic acid Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- 239000004160 Ammonium persulphate Substances 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 230000000274 adsorptive effect Effects 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 229930182470 glycoside Natural products 0.000 claims description 4
- 150000002338 glycosides Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000033444 hydroxylation Effects 0.000 claims description 4
- 238000005805 hydroxylation reaction Methods 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 3
- 238000002474 experimental method Methods 0.000 claims description 3
- 210000005077 saccule Anatomy 0.000 claims description 3
- 150000003384 small molecules Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000012512 characterization method Methods 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920006254 polymer film Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 3
- 150000001298 alcohols Chemical class 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 229940048053 acrylate Drugs 0.000 description 48
- 238000010521 absorption reaction Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 6
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 5
- 229940047670 sodium acrylate Drugs 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000012528 membrane Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 241000237502 Ostreidae Species 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 235000020636 oyster Nutrition 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 235000009847 Cucumis melo var cantalupensis Nutrition 0.000 description 1
- 244000241200 Cucumis melo var. cantalupensis Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- -1 ethanol alcohols Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000001257 hydrogen Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Abstract
The invention discloses a [5] turil bridged acrylic polymer microsphere, a preparation method and an application. The [5] turil bridged acrylic polymer microsphere is characterized in that the [5] turil bridged acrylic polymer microsphere is synthesized by reacting[5] turil as a crosslinking agent, acrylic acid as a monomer, and ammonium persulfate as an oxidizing agent and also an initiating agent, in water. The method has the advantages of simplicity in synthesis, high yield, easiness and simplicity in operation, short cycle and the like. The microsphere has a better preferential adsorption function on polar small organic molecules, particularly volatile alcohol small organic molecules, and can be used for preferential adsorption and separation of volatile alcohols such as methanol and ethanol.
Description
Technical field
The present invention is a kind of five yuan of melon ring bridging acrylate copolymer microballoons and preparation method and application, belongs to modification melon loop technique field.Utilize that five yuan of melon rings are cross linking agent, vinylformic acid is monomer specifically, ammonium persulphate synthesizes five yuan of melon cyclic group bridging acrylate copolymer microballoons for the method that oxygenant is also initiator simultaneously, and for selective adsorption organic molecule gas material.
Background technology
The fields such as porous material is studied in class micro-pore zeolite usually, mesoporous silicon oxide, metal oxide, the polymkeric substance of metal-organic framework compound (MOF) and macropore.They are all obtaining developing very widely from structured material to energy technology, and in catalysis, absorption, is used widely in the aspects such as ion-exchange and Supramolecular self assembly body.
Usually, melon cyclic group polymkeric substance will pass through: 1) melon epoxy turns to hydroxyl melon ring; 2) introducing monomer is modified by hydroxyl melon ring again; 3) finally synthesized by monomer polymerization three one step process.But it is very large melon epoxy to be turned to the loss such as hydroxyl melon ring and later further derivatize.The melon cyclic group polymkeric substance based on hydroxyl melon ring reported at present is mainly based on hexa-atomic melon ring, although five yuan of melon ring hydroxylation yields are a little less than hexa-atomic melon ring (<42%), but the port diameter less due to five yuan of melon rings and cavity, general few people study;
This patent adopts one kettle way, and hydroxylation and derivatize two processes are carried out in same reactor simultaneously, and avoid meaningless loss, productive rate is greater than 50%, and five yuan of melon rings are effectively utilized.The port diameter less due to five yuan of melon rings and cavity, can not the general organic molecule of inclusion, about they are (Q [5] and SQ [5] host-guest chemistry research report s) seldom, except some are as gas molecules such as methane, ethane, acetylene.And five yuan of melon cyclic group polymkeric substance likely provide the analysis test platform to these gas molecules highly selectivies just.In addition, by melon ring coordination chemistry aspect research in recent years, five yuan of melon rings due to melon central port less, ketonic oxygen distribution density is high, can form title complex with each metal ion species generation coordination.And for different metal ions, its ability to function has obvious difference.Be not why because five yuan of melon rings have well water-soluble with five yuan of melon rings as parting material, do not have effective means to be separated from solution by the title complex that itself and metal ion are formed.But five yuan of melon cyclic group polymkeric substance, five yuan of melon cyclic group polymkeric substance particularly after solidification then likely carry out the research of this respect.
Before this, our experimental group has applied for five yuan, hexa-atomic or eight yuan of melon ring bridging acrylate copolymer and preparation method's (application number: 201410394061.O), the five yuan of melon ring bridging acrylate copolymer obtained are sheet like membrane structure, to small molecules organic gas without adsorption.
Present patent application is selected, in water, utilize that five yuan of melon rings are cross linking agent, vinylformic acid is monomer, ammonium persulphate synthesizes five yuan of melon cyclic group bridging acrylate copolymer microballoons for the method that oxygenant is also initiator simultaneously, experiment shows, this material has stronger selective adsorption effect to polarity organic molecule especially volatile alcohol organic micromolecule base.The novel nano-material with functions such as selective adsorption, trapping, separation, catalytic reaction, medium sensors can be become.
Summary of the invention
The object of the invention is to synthesize five yuan of melon cyclic group bridging acrylate copolymer microballoons, a kind of microspheroidal imitated vesicle structure, is a kind of new shape of five yuan of melon ring bridging acrylate copolymer, has new character, to organic molecule, there is selective adsorption, disclose its synthetic method.Utilize five yuan of melon cyclic group bridging acrylate copolymer micro-sphere material ducts and surface to volatility organic molecule (methyl alcohol, ethanol, acetone, tetracol phenixin, the acetonitrile) characteristic that adsorptivity is different, can be used for the selectivity trapping of organic molecule, absorption or separation etc.
The present invention's five yuan of melon ring bridging acrylate copolymer microballoons, be with five yuan of melon rings be cross linking agent, vinylformic acid is monomer, ammonium persulphate synthesizes five yuan of melon cyclic group bridging acrylate copolymer microballoons for the method that oxygenant is also initiator simultaneously, five yuan of melon rings in molar ratio: ammonium peroxydisulfate: prepare burden in vinylformic acid=1:5:40 ~ 80, adopt " one kettle way " reaction, obtain a kind of five yuan of melon ring bridging acrylate copolymer microballoon novel materials, its structural formula is as follows:
Five yuan of described melon ring bridging acrylate copolymer microballoons, be solid white powder, be slightly soluble in water, when 20 DEG C, solubleness is 0.213g/L, is insoluble to organic solvent.According to vinylformic acid, the proportioning of five yuan of melon rings is different, and microsphere diameter is 500-800 nanometer, and microballoon has the characterization of adsorption to volatility organic molecule gas, different to different volatility organic molecule gas adsorption amounts.
Above-mentioned five yuan of melon ring bridging acrylate copolymer microballoons, only have the percentage of grafting when polyacrylic acid methyne of glycosides urea in five yuan of melon rings enough large, the length sufficiently long of polyacrylic acid chain just can be formed with the polymer film structure of certain curvature radius thus form polymer microballoon, by a series of orthogonal experiment, draw when five yuan of melon rings, when Potassium Persulfate mol ratio is 1:5, when making the percentage of grafting of polyacrylic acid methyne of glycosides urea in five yuan of melon rings reach 0.4, by controlling adding of Acrylic Acid Monomer, namely acrylic acid amount reaches vinylformic acid, five yuan of melon ring mol ratios are 40 ~ 80:1, available five yuan of melon ring melon ring bridging acrylate copolymer microballoons.
Five yuan of described melon ring bridging acrylate copolymer microballoons, only have when five yuan of melon rings, when Potassium Persulfate mol ratio is 1:5, when five yuan of melon rings, when vinylformic acid mol ratio is 1:40, its pattern is diameter is 500-600 nm saccule bubble structure: when five yuan of melon rings, when vinylformic acid mol ratio is 1:80, microsphere diameter is 700-800 nm.
Five yuan of described melon ring bridging acrylate copolymer microballoons, it is utilize five yuan of bridging acrylate copolymer micro-sphere material ducts and surface to volatility organic molecule gas: the characteristic that the adsorptive capacity of methyl alcohol, ethanol, acetone, tetracol phenixin or acetonitrile is different, can record according to test, 20 DEG C, 101kPa time, 1g five yuan of adsorbable methyl alcohol 0.212g of bridging acrylate copolymer microballoon, ethanol 0.08g, acetone 0.053g, tetracol phenixin 0.052g, acetonitrile 0.029g.
The preparation method of the present invention's five yuan of bridging acrylate copolymer follows these steps to respectively carry out:
The preparation method of five yuan of melon ring bridging acrylate copolymer microballoons
(1) five yuan of melon ring Q [5] and ammonium peroxydisulfate APS are weighed by proportioning, five yuan of melon rings and ammonium peroxydisulfate APS are mixed in adding distil water in there-necked flask and dissolve, stir, logical 15min nitrogen under room temperature;
(2) there-necked flask temperature be elevated to 70 DEG C and be incubated 1h;
(3), after completing steps (2), in there-necked flask, slowly AA is dripped according to Q [5] and the ratio of Acrylic Acid Monomer AA mol ratio 1:40 ~ 80, after dripping, reacting by heating 4 ~ 5h under 70 DEG C of conditions;
(4) after question response completes, take off there-necked flask, solution is placed room temperature, decompress filter removes impurity, gets the small-molecule substance that clear liquid uses the dialysis tubing of molecular weight 2000 to dialyse in flowing water environment in 24h removal solution;
(5) by the solution decompression dephlegmate after dialysis well, in the solid matter stayed, add acetone, add 100mL acetone by every 1g five yuan of melon ring raw materials, soak more than 4h and remove homopolymer;
(6) with dry sand core funnel decompress filter, get solid and be placed in 45 DEG C of baking ovens and dry, obtain product.
Five yuan of melon ring bridging acrylate copolymer microballoons, its formation mechenism is the webbed five yuan of melon ring bridging acrylate copolymer of hydroxyl radical reaction shape when polyacrylic acid chain free radical and five yuan of melon rings, hydrogen bond action is passed through by the ketonic oxygen of five yuan of melon central ports and acrylic acid carboxyl between five yuan of netted melon ring bridging acrylic polymer layer and layer, polymkeric substance is coupled together between layers, form five yuan of melon ring bridging acrylate copolymer membrane structures, because the energy requirement of membrane structure self tends towards stability, the micro-sphere structure that final forming energy is the most stable.
The preparation method of five yuan of melon ring bridging acrylate copolymer microballoons of the present invention, is hydroxylation and derivative reaction, reacts successively in same reaction vessel, and namely " one kettle way " reaction, makes five yuan of melon ring bridging acrylate copolymer microballoon productive rates be greater than 50%.
The application of the adsorption selection material of five yuan of bridging acrylate copolymer micro-sphere materials of the present invention, is characterized in that the selectivity for organic molecule traps, adsorbs, is separated, to the analysis test platform of these gas molecules highly selectivies.Due to comparatively large to the adsorptive capacity of methyl alcohol or ethanol, and less or do not adsorb to the adsorptive capacity that other organic gas is micromolecular, can be used as being separated.
The present invention is the further research and development of this seminar patent application (201410394061.O), obtain a kind of five yuan of bridging acrylate copolymer of different shape, namely five yuan of melon ring bridging acrylate copolymer of saccule bubble structure, have studied the synthetic method of this material.Meanwhile, utilize this kind of five yuan of melon ring bridging acrylate copolymer microballoon features, the selective adsorption that can be used for alcohols as volatile in methyl alcohol, ethanol etc. be separated.
Accompanying drawing explanation
Fig. 1 five yuan of melon ring bridging acrylate copolymer microballoon reaction schematic diagram.
Fig. 2 five yuan of melon ring bridging vinylformic acid nuclear magnetic spectrograms.
Fig. 3 five yuan of melon ring bridging acrylate copolymer microballoon transmission electron microscope pictures and scanning electron microscope (SEM) photograph
Fig. 4 five yuan of melon ring bridging acrylate copolymer microballoons are to the adsorption curve of multiple volatility organic molecule.
Fig. 5 five yuan of melon ring bridging acrylate copolymer microballoons and five yuan of melon ring powder are to the absorption property life test of methyl alcohol.
Fig. 6 five yuan of melon ring bridging acrylate copolymer microballoons, five yuan of melon ring powder, sodium acrylate powder are to the absorption curve of methyl alcohol, show five yuan of melon ring bridging acrylate copolymer microballoons and have good assimilation effect to methyl alcohol, specific absorption about 20.8% than pure five yuan of melon ring powder.
Fig. 7 five yuan of melon ring bridging acrylate copolymer microballoons, five yuan of melon ring powder, sodium acrylate powder are to the absorption curve of ethanol, show five yuan of melon ring bridging acrylate copolymer microballoons relatively better to ethanol assimilation effect than pure five yuan of melon ring powder, specific absorption about 8%.
Fig. 8 five yuan of melon ring bridging acrylate copolymer microballoons, five yuan of melon ring powder, sodium acrylate powder are to the absorption curve of acetone, show five yuan of melon ring bridging acrylate copolymer microballoons relatively better to the assimilation effect of acetone than pure five yuan of melon ring powder, specific absorption about 5.3%.
Fig. 9 five yuan of melon ring bridging acrylate copolymer microballoons, five yuan of melon ring powder, sodium acrylate powder are to the absorption curve of tetracol phenixin, show five yuan of melon ring bridging acrylate copolymer microballoons relatively poor to the assimilation effect of tetracol phenixin than pure five yuan of melon ring powder, specific absorption about 5.18%.
Figure 10 five yuan of melon ring bridging acrylate copolymer microballoons, five yuan of melon ring powder, sodium acrylate powder are to the absorption curve of acetonitrile, show five yuan of melon ring bridging acrylate copolymer microballoons relatively consistent to the assimilation effect of acetonitrile than pure five yuan of melon ring powder, specific absorption about 2.85%.
Draw from above-mentioned absorption result, five yuan of melon ring bridging acrylate copolymer microballoons show obvious absorption selectivity to the volatility such as methyl alcohol, ethanol alcohols.
specific implementation method
The specific implementation method of five yuan of melon ring bridging acrylate copolymer
Example one:
(1) five yuan of melon ring 1g(0.1nmol are taken respectively), ammonium peroxydisulfate 1.13g(0.5nmol) add in 250ml there-necked flask, in bottle, add 50ml distilled water, put into magnetic stir bar, pass into nitrogen protection, stir at normal temperatures, now for oyster white is suspended liquid;
(2) after 5min, there-necked flask temperature is raised to 70 DEG C, insulation 1h, in reaction process, reaction solution becomes more as clear as crystal gradually;
(3), after completing steps (2), slowly drip 100mL 0.4mol/L(4nmol with dropping funnel) vinylformic acid, drip speed be about per minute 5 ~ 10, after dripping, reacting by heating 4 ~ 5h under 70 DEG C of conditions;
(4) after question response completes, take off there-necked flask, cool to room temperature, filter, get clear liquid, use the dialysis tubing of molecular weight 2000 to carry out dialysis 24h in flowing water environment;
(5) solution after dialysis is well spin-dried for, adds 100ml more than acetone soak 4h;
(6) remove acetone with dry sand core funnel decompress filter, in the vacuum drying oven that temperature is 40 DEG C, dry solids, levigately namely obtain five yuan of melon cyclic group bridging acrylate copolymer microballoon 1.12g.Productive rate is that 72.54%(is with melon ring note).
Example two:
(1) five yuan of melon ring 1g(0.1nmol are taken respectively), ammonium peroxydisulfate 1.13g(0.5nmol) add in 250ml there-necked flask, in bottle, add 50ml distilled water, put into magnetic stir bar, pass into nitrogen protection, stir at normal temperatures, now for oyster white is suspended liquid;
(2) after 5min, there-necked flask temperature is raised to 70 DEG C, insulation 1h, in reaction process, reaction solution becomes more as clear as crystal gradually;
(3), after completing steps (2), slowly drip 200mL 0.4mol/L(8nmol with dropping funnel) vinylformic acid, drip speed be about per minute 5 ~ 10, after dripping, reacting by heating 4 ~ 5h under 70 DEG C of conditions;
(4) after question response completes, take off there-necked flask, cool to room temperature, filter, get clear liquid, use the dialysis tubing of molecular weight 2000 to carry out dialysis 24h in flowing water environment;
(5) solution after dialysis is well spin-dried for, adds 100ml more than acetone soak 4h;
(6) remove acetone with dry sand core funnel decompress filter, solids is dry in the vacuum drying oven of 40 DEG C in temperature, levigately namely obtains five yuan of melon cyclic group bridging acrylate copolymer solid 1.65g.Productive rate is that 69.37%(is with melon ring note).
Claims (7)
1. five yuan of melon ring bridging acrylate copolymer microballoons, it is characterized in that with five yuan of melon rings be cross linking agent, vinylformic acid is monomer, ammonium persulphate synthesizes five yuan of melon cyclic group bridging acrylate copolymer microballoons for the method that oxygenant is also initiator simultaneously, five yuan of melon rings in molar ratio: ammonium peroxydisulfate: prepare burden in vinylformic acid=1:5:40 ~ 80, adopt " one kettle way " reaction, obtain a kind of five yuan of melon ring bridging acrylate copolymer microballoon novel materials, its structural formula is as follows:
Five yuan of described melon ring bridging acrylate copolymer microballoons, for solid white powder, be slightly soluble in water, when 20 DEG C, solubleness is 0.213g/L, be insoluble to organic solvent, according to vinylformic acid, the proportioning of five yuan of melon rings is different, and microsphere diameter is 500-800 nanometer, microballoon has the characterization of adsorption to volatility organic molecule gas, different to different volatility organic molecule gas adsorption amounts.
2. five yuan of melon ring bridging acrylate copolymer microballoons according to claim 1, it is characterized in that only having the percentage of grafting when polyacrylic acid methyne of glycosides urea in five yuan of melon rings enough large, the length sufficiently long of polyacrylic acid chain just can be formed with the polymer film structure of certain curvature radius thus form polymer microballoon, by a series of orthogonal experiment, draw when five yuan of melon rings, when Potassium Persulfate mol ratio is 1:5, when making the percentage of grafting of polyacrylic acid methyne of glycosides urea in five yuan of melon rings reach 0.4, by controlling adding of Acrylic Acid Monomer, namely acrylic acid amount reaches vinylformic acid, five yuan of melon ring mol ratios are 40 ~ 80:1, available five yuan of melon ring melon ring bridging acrylate copolymer microballoons.
3. five yuan of melon ring bridging acrylate copolymer microballoons according to claim 1, it is characterized in that five yuan of melon rings, when Potassium Persulfate mol ratio is 1:5, when five yuan of melon rings, when vinylformic acid mol ratio is 1:40, its pattern is diameter is 500-600 nm saccule bubble structure: when five yuan of melon rings, when vinylformic acid mol ratio is 1:80, its microsphere diameter is 700-800 nm.
4. five yuan of melon ring bridging acrylate copolymer microballoons according to claim 1, it is characterized in that utilizing five yuan of bridging acrylate copolymer micro-sphere material ducts and surface to volatility organic molecule gas: the characteristic that the adsorptive capacity of methyl alcohol, ethanol, acetone, tetracol phenixin or acetonitrile is different, can record according to test, 20 DEG C, 101kPa time, 1g five yuan of adsorbable methyl alcohol 0.212g of bridging acrylate copolymer microballoon, ethanol 0.08g, acetone 0.053g, tetracol phenixin 0.052g, acetonitrile 0.029g.
5. the preparation method of five yuan of bridging acrylate copolymer as claimed in claim 1, is characterized in that following these steps to respectively carry out:
The preparation method of five yuan of melon ring bridging acrylate copolymer microballoons
Five yuan of melon ring Q [5] and ammonium peroxydisulfate APS are weighed by proportioning, five yuan of melon rings and ammonium peroxydisulfate APS is mixed in adding distil water in there-necked flask and dissolves, stir, logical 15min nitrogen under room temperature;
(2) there-necked flask temperature be elevated to 70 DEG C and be incubated 1h;
(3), after completing steps (2), in there-necked flask, slowly AA is dripped according to Q [5] and the ratio of Acrylic Acid Monomer AA mol ratio 1:40 ~ 80, after dripping, reacting by heating 4 ~ 5h under 70 DEG C of conditions;
(4) after question response completes, take off there-necked flask, solution is placed room temperature, decompress filter removes impurity, gets the small-molecule substance that clear liquid uses the dialysis tubing of molecular weight 2000 to dialyse in flowing water environment in 24h removal solution;
(5) by the solution decompression dephlegmate after dialysis well, in the solid matter stayed, add acetone, add 100mL acetone by every 1g five yuan of melon ring raw materials, soak more than 4h and remove homopolymer;
(6) with dry sand core funnel decompress filter, get solid and be placed in 40 DEG C of baking ovens and dry, obtain product.
6. the preparation method of five yuan of melon ring bridging acrylate copolymer microballoons according to claim 5, it is characterized in that hydroxylation and derivative reaction, react successively in same reaction vessel, namely " one kettle way " reaction, makes five yuan of melon ring bridging acrylate copolymer microballoon productive rates be greater than 50%.
7. the application of the adsorption selection material of five yuan of bridging acrylate copolymer micro-sphere materials as described in claim 1 or 4, is characterized in that the selectivity for organic molecule traps, adsorbs, is separated, to the analysis test platform of these gas molecules highly selectivies.
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